EP0675107A1 - Herstellung von Alkansulfonylchloriden und Alkansulfonsäuren unter Druck - Google Patents
Herstellung von Alkansulfonylchloriden und Alkansulfonsäuren unter Druck Download PDFInfo
- Publication number
- EP0675107A1 EP0675107A1 EP95104523A EP95104523A EP0675107A1 EP 0675107 A1 EP0675107 A1 EP 0675107A1 EP 95104523 A EP95104523 A EP 95104523A EP 95104523 A EP95104523 A EP 95104523A EP 0675107 A1 EP0675107 A1 EP 0675107A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- reactor
- rsx
- compound
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/16—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups
Definitions
- This invention is a process for the production of content along with the coproduction of alkanesulfonyl chloride (ASC) and/or alkanesulfonic acid (ASA), wherein a compound of the formula RSX, X being hydrogen or -SR1 and R and R1 are alkyl groups, is reacted with chlorine in an aqueous hydrochloric acid medium at an elevated pressure. More particularly, it relates to the process of reacting an alkyl mercaptan or alkyl disulfide with chlorine in an aqueous hydrogen chloride medium at a temperature of from about -10 to about 115°C and at a pressure of at least 1.05 atmospheres (absolute) up to 81.6 atm. abs.
- alkanesulfonyl chloride ASC
- alkanesulfonic acid ASA
- mixtures thereof by reacting an alkyl mercaptan or an alkyl disulfide with chlorine in an aqueous hydrochloric acid medium at a reaction temperature ranging from about -10° up to about 115°C.
- incondensible hydrogen chloride vapor is produced and passes upward with water vapor and some entrained ASA and/or ASC into a condenser where it is removed overhead.
- Entrained ASA is present as an aerosol while entrained ASC is a combination of ASC vapors (major contributor) and ASC aerosol (minor contributor).
- References disclosing these processes include, for example, U.S. Patent No. 3,626,004 issued December 7, 1971, U.S. Patent No. 3,600,136 issued August 17, 1971 and U.K. Patent No. 1,350,328 published April 18, 1974.
- the prior art teaches that it is desirable to carry out the described processes at or below atmospheric pressure to facilitate overhead removal of gaseous products from the reactor. It is taught that residual hydrogen chloride, along with other volatile impurities, can be removed from the ASC and/or ASA products by vacuum or steam stripping.
- the hydrogen chloride vapor co-produced overhead in accordance with the prior art methods contains significant quantities [thousands of parts per million (ppm] of ASC, due to the stripping effect of hydrogen chloride vapor emerging from the reactor.
- ppm parts per million
- ASC is decomposed by the presence of ferrous ions, releasing objectionable odors. Consequently, it is necessary to further treat the hydrochloric acid coproduct to decrease its ASC levels to reduce or eliminate its odor-forming tendency.
- This invention is a process for the continuous preparation of alkanesulfonyl chloride or alkanesulfonic acid comprising reacting a compound of the formula RSX, where X is hydrogen or the radical -SR1 and R and R1 are alkyl groups having from 1 to 20 carbon atoms, with chlorine in an aqueous hydrogen chloride medium at a temperature ranging from -10 to 115°C, and at a pressure of 1.05 atmospheres (atm.) absolute (abs.), or about 1.04 bars, up to 81.6 atm. abs., or about 80.54 bars.
- the process disclosed herein involves a pressurized reaction of a compound of the formula RSX where X is hydrogen or the radical -SR1 and R and R1 are alkyl groups having from 1 to 20 carbon atoms, preferably from 1 to 8 carbon atoms including, for example, methyl, ethyl, propyl, butyl, hexyl and octyl.
- the compounds represented by RSX are alkyl mercaptans and alkyl disulfides.
- the RSX compound is reacted with chlorine gas in an aqueous hydrogen chloride medium, preferably concentrated hydrochloric acid. While the reaction may be initiated in pure water or dilute hydrochloric acid, the aqueous medium will shortly become concentrated hydrochloride acid due to the evolution of gaseous hydrogen chloride in the aqueous medium from the reaction of the RSX compound and chlorine.
- the feedrate of the RSX compound to the pressurized reaction ranges from 0.005 to 12 pound-mole per hour-foot squared (lbmole/hr.-ft2) of cross-sectional area of the "active" zone of the reactor, more preferably, from 0.5 to about 8.0 lbmole/ hr.-ft.2.
- This reaction when carried out at a temperature within the range of -10 to 50°C, preferably 10 to 35°C, produces predominantly an ASC product with hydrogen chloride recovered overhead. At temperatures in the range of 85°C to 115°C, preferably 95 to 110°c, this reaction produces predominantly ASA coproduct with a small amount of ASC. A distinct mixture of ASC and ASA is obtained when the reaction temperature is between 50 and 85°C.
- the process described above is unexpectedly improved by operation under pressure, and where the equipment is modified to permit the reaction to run under pressurized conditions.
- the pressure under which the process is run ranges from 1.05 atm. abs., or about 1.06 bars, up to 81.6 atm. abs. or about 82.7 bars (the critical pressure of HCl).
- the reaction pressure will range from about 1.6 atm. abs. up to about 10 atm. abs., more preferably, from 1.1 to 5 atm. abs.
- the process of this invention provides an unexpected improvement in gas-liquid contact and solubilization of the reactant gases, improving raw material utilization in the reactor.
- the process also has the unexpected effect of reducing the amount of liquid that can condense-out of the vapor emerging from the reactor (one would normally expect an increase in the amount of condensibles as pressure is increased) . This allows the reactor to use smaller less costly auxiliary systems such as condensers and pumps.
- the process of this invention operated at super atmospheric pressure, even with only a moderate elevation in pressure, significantly reduces the contamination of the HCl co-product by ASC, i.e. pressurized operation mitigates the stripping effect of the HCl vapor emerging from the reactor.
- Pressurized operation also improves the volumetric efficiency of the reactor, by increasing the liquid fraction in the ebulliating zone (zone of reactor in which the reaction of RSX with chlorine produces turbulence), increasing the effective residence time, or conversely, increasing the allowable throughput at a given residence time. Pressurization also promotes disengagement of the vapor from the liquid, reducing the likelihood of entraining liquid with the gaseous co-product. This, in turn, increases the practical upper limit on the reactor throughput before hydrodynamic effects (e.g., foaming, entrainment) limit reactor capacity.
- hydrodynamic effects e.g., foaming, entrainment
- a liquid crude product On formation of a liquid crude product (ASC, ASA or mixtures thereof) it is depressurized to atmospheric or sub-atmospheric pressure, preferably at or above the reaction temperature, to devolatilize the additional hydrogen chloride that goes into solution as a result of the pressurized operation.
- the depressurized crude liquid reaction product is treated further, as described in the known art, to remove residual impurities.
- the HCl vapor liberated by the depressurization step is removed overhead and may be processed further by conventional means, to recover and/or further purify the HCl.
- the vapors and gases exiting the top of the reactor pass to a condenser.
- the condensed liquid leaving the condenser is returned to the reactor.
- the HCl and other non-condensible gases e.g., inerts, excess chlorine, or other gaseous reaction products
- the non-condensible gases may be processed further by conventional means, to recover, separate and/or further purify them.
- a fractionation column is interposed between the reactor and the condenser, as follows:
- the vapors and gases exiting the top of the reactor are sent to the bottom vapor inlet of a (pressurized) rectification column (e.g., packed or trayed fractionator).
- a (pressurized) rectification column e.g., packed or trayed fractionator.
- the vapors are contacted with cooled condensed liquid, returning from the condenser, effecting a separation reducing (by distillative action) the residual concentration of less volatile species (such as ASC) in the vapor stream.
- the purified vapor stream exits the top of the rectification column and is passed to a condenser.
- the condensed liquid leaving the condenser is returned as reflux to the top liquid inlet of the rectification column.
- the condensed liquid leaving the bottom of the rectification column is recycled to the reactor.
- the HCl and other non-condensible gases e.g., inerts, excess chlorine, or other gaseous reaction products
- the non-condensible gases may be processed further by conventional means, to recover, separate and/or purify them.
- the apparatus described below was used in the following Examples 1-4:
- the apparatus comprised a vertical tubular 4" internal diameter reactor constructed of sections of glass, glass-lined steel, and fluoropolymer-lined steel flanged pipe fittings (spools, tees, and crosses), with an overall length of 14 feet.
- the reactor was connected to an adjacent vertical ("side-arm") heat exchanger by means of an overflow conduit about 12 feet up from the bottom of the reactor, and by a recycle conduit about 2 feet above the bottom of the reactor.
- the reactor was configured for continuous operation.
- methanesulfonic acid methanesulfonyl chloride may be similarly prepared
- the system was charged with a mixture containing about 70 vol % methanesulfonic acid (MSA), 26% water, and 4% hydrogen chloride (HCl).
- MSA methanesulfonic acid
- HCl hydrogen chloride
- the reactor was filled to about 1 foot below the overflow conduit.
- Chlorine gas 99.5% pure
- Vaporized methyl mercaptan (99 % pure) was sparged into the reactor on automatic flow control via a feed port about 5 feet from the bottom of the reactor (a drilled fluoropolymer feed tube extending across the cross-section of the reactor served as the sparger).
- the gas evolution created bubbles which expanded the reaction liquid above the level of the overflow conduit, inducing a circulation through the side-arm exchanger, which was used to remove the exothermic heat of reaction.
- Coolant flow to the side-arm exchanger was adjusted by an automatic temperature controller, to maintain the temperature of the (cooled) liquid recirculating to the reactor at the target temperature.
- the reactor was operated above 80°C, so that the primary reaction product was the sulfonic acid (MSA), with a minor percentage of unhydrolyzed methanesulfonyl chloride (MSC)] which may be hydrolyzed to MSA by heating in the presence of water, e.g. in the steam stripping operation for MSA.
- MSA sulfonic acid
- MSC unhydrolyzed methanesulfonyl chloride
- a portion of the recirculating reaction liquid was taken-off on automatic flow control via the bottom of the reactor as crude MSA product.
- the take-off rate was adjusted to maintain the target specific gravity.
- the liquid level in the reactor was maintained at about 2 inches above the overflow conduit, by feeding make-up water to the reactor on automatic level control.
- the makeup water was combined with the recycle condensate and introduced to the reactor via a liquid feed port about 2 1/2 feet above the bottom of the reactor.
- the "active" zone of the reactor was the 7 foot long section of the reactor between the mercaptan feed port and the overflow conduit to the heat exchanger.
- the bottom 5 feet of the "active” zone was constructed of glass piping, to allow visual observation of the bubble dynamics in the active zone.
- the reaction temperature was 113 °C.
- the reactor top pressure was 1.5 psig (1.10 atm. abs.).
- the mercaptan feedrate was 5.6 lb/hr, and the chlorine feedrate was 24.8 lb/hr, corresponding to 0.44% excess chlorine.
- the crude take-off rate was adjusted to maintain the specific gravity of the reaction liquid at 1.38, corresponding to about 76 wt. % MSA in the crude product.
- Example 1a the operating conditions were identical to Example 1a, except that the reaction was carried-out at a pressure of 11 psig (1.75 atm. abs.).
- the reaction temperature was 113°C.
- the reactor top pressure was 1.5 psig (1.10 atm. abs.).
- the mercaptan feedrate was 5.6 lb/hr., and the chlorine feedrate was 25.5 lb/hr., corresponding to 3.28% excess chlorine.
- the crude take-off rate was adjusted to maintain the specific gravity of the reaction liquid at 1.38, corresponding to about 76 wt. % MSA in the crude product.
- Example 2a the operating conditions were identical to Example 2a, except that the reaction was carried-out at a pressure of 11 psig (1.75 atm. abs.).
- the reaction temperature was 113°C.
- the reactor top pressure was 20.5 psig (2.40 atm. abs.).
- the mercaptan feedrate was 5.6 lb/hr. and the chlorine feedrate was 25.5 lb/hr, corresponding to 3.28% excess chlorine.
- the crude take-off rate was adjusted to maintain the specific gravity of the reaction liquid at 1.30, corresponding to about 58 wt. % MSA in the crude product.
- Example 3a it was attempted to duplicate the operating conditions of Example 3a, except that the reaction was carried-out at a pressure of 0.1 psig (1.00 atm. abs.).
- Example 1a The flowrates of the condensed vapors being returned to the reactor in the examples above were measured with a rotameter.
- Example 1b At the operating conditions of Example 1a (1.5 psig), the average condensate flow was about 20 lb/hr.
- Example 1b At the operating conditions of Example 1b (11 psig), the average condensate flow was about 10-15 lb/hr.
- the following example is set forth to demonstrate the use of a fractionating or rectifying column in the manufacture of ASC and ASA.
- the interposition of a fractionator between the reactor and condenser unexpectedly greatly decreases the amount of ASC entrained in the hydrogen chloride byproduct gases.
- This fractionating system will function advantageously with the superatmospheric pressure reaction of this invention as well as with vacuum and normal atmospheric pressure reactions of the prior art for the continuous preparation of alkanesulfonyl chloride and alkanesulfonic acid by the reaction of an alkyl mercaptan or alkyl disulfide with chlorine under the temperature conditions described herein.
- the following experiments were conducted at atmospheric pressure in the reactor.
- the object of the following experiments was to determine the effectiveness of the several systems to reduce and recover entrained MSC.
- a reactor was used consisting of a 500 ml., three-neck flask filled with 200 ml. of 36% aqueous hydrochloric acid (HCl) and 200 ml. of methanesulfonyl chloride (MSC). Mounted vertically atop the reactor flask and attached to one of the three necks was one of three types of tubular columns described hereinafter.
- the second neck was connected to a sintered glass frit of course porosity which sparged anhydrous HCl through a rotameter mounted atop an HCl supply cylinder into the reactor to simulate the HCl evolution which occurs during the reaction of methyl mercaptan with gaseous chlorine, in a concentrated aqueous HCl media.
- the HCl feed rate to the reactor was 1.57 l./min. (0.07 moles/min. or 2.5 grams/min.).
- the third neck of the flask was used to supply the aqueous HCl and MSC to the reaction
- the tubular column attached vertically to the top of the reactor was an open column 60 cm. in length by 2.5 cm. in diameter.
- the tubular column was of the same size as in experiment A but was packed with 0.5 cm ceramic saddles (functions as a crude fractionator).
- the column was a 30 tray Oldershaw column.
- experiment A all entrained material entered the top of the HCl absorber from the open tubular column.
- 2.09g of MSC was dissolved in 441 g. of 32% HCl.
- the MSC concentration was 4751 parts per million (ppm) in the 32% concentrated aqueous HCl.
- the 2.09 g. of MSC was liberated by 141 of HCl gas which indicates an MSC concentration of 0.0148 g. of MSC per g. of HCl gas.
- experiment B the same conditions were established as in experiment A but the open tubular column was packed with 0.5 cm. ceramic saddles and reflux was established. The reflux was slight, ⁇ 0.5 ml/min.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US221222 | 1980-12-30 | ||
US22122294A | 1994-03-31 | 1994-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0675107A1 true EP0675107A1 (de) | 1995-10-04 |
Family
ID=22826902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95104523A Withdrawn EP0675107A1 (de) | 1994-03-31 | 1995-03-28 | Herstellung von Alkansulfonylchloriden und Alkansulfonsäuren unter Druck |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0675107A1 (de) |
JP (1) | JPH0841011A (de) |
CN (1) | CN1112110A (de) |
BR (1) | BR9501297A (de) |
CA (1) | CA2145325A1 (de) |
HU (1) | HUT71090A (de) |
IL (1) | IL113125A0 (de) |
PL (1) | PL307952A1 (de) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0894765A1 (de) * | 1997-07-31 | 1999-02-03 | Elf Atochem S.A. | Reinigung von Salzsäure, Nebenprodukt der Methansulfonsäureherstellung |
WO2002010123A1 (de) * | 2000-08-01 | 2002-02-07 | Basf Aktiengesellschaft | Verfahren zur herstellung von alkylsulfonylchloriden und/oder alkansulfonsäuren |
CN1769160B (zh) * | 2004-06-30 | 2010-05-05 | 阿克马公司 | 甲磺酸合成中副产物盐酸的纯化方法 |
EP2386372A2 (de) | 2005-09-22 | 2011-11-16 | ATI Properties, Inc. | Vorrichtung für reine, schnell verfestigte Legierungen |
WO2017080994A1 (de) | 2015-11-10 | 2017-05-18 | Basf Se | Verfahren zur wiederaufarbeitung von alkansulfonsäure |
WO2018192954A1 (en) | 2017-04-18 | 2018-10-25 | Basf Se | Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride |
WO2018219726A1 (en) | 2017-05-30 | 2018-12-06 | Basf Se | Process for the production of alkanesulfonic acids |
WO2019154681A1 (en) | 2018-02-07 | 2019-08-15 | Basf Se | Process for the manufacturing of alkanesulfonic acids |
US10577312B2 (en) | 2015-11-10 | 2020-03-03 | Basf Se | Process for purifying alkanesulfonic acids |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101863803B (zh) * | 2010-06-10 | 2013-04-24 | 湖北星火化工有限公司 | 一种副产盐酸的纯化方法 |
CN106866469A (zh) * | 2017-01-18 | 2017-06-20 | 湖北星火化工有限公司 | 甲基磺酸尾气的处理方法 |
CN111909062A (zh) * | 2019-05-10 | 2020-11-10 | 乌海市兰亚化工有限责任公司 | 一种采用微通道反应器制备甲基磺酰氯的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3600136A (en) * | 1968-08-26 | 1971-08-17 | Stauffer Chemical Co | Apparatus for producing methane sulfonyl chloride |
US3626004A (en) * | 1967-12-07 | 1971-12-07 | Pennwalt Corp | Method of preparing alkyl sulfonyl chloride |
GB1350328A (en) * | 1971-05-28 | 1974-04-18 | Pennwalt Corp | Method for the preparation of alkane sulphonic acids |
US3993692A (en) * | 1966-01-03 | 1976-11-23 | Stauffer Chemical Company | Methane sulfonyl chloride and process of preparation |
EP0040560A1 (de) * | 1980-05-16 | 1981-11-25 | Societe Nationale Elf Aquitaine (Production) | Herstellung von Alkan-Sulfonyl-Chloriden |
EP0319767A2 (de) * | 1987-12-05 | 1989-06-14 | Bayer Ag | Verfahren zur Herstellung von Trifluormethansulfonsäurechlorid |
-
1995
- 1995-03-23 CA CA002145325A patent/CA2145325A1/en not_active Abandoned
- 1995-03-24 IL IL11312595A patent/IL113125A0/xx unknown
- 1995-03-28 EP EP95104523A patent/EP0675107A1/de not_active Withdrawn
- 1995-03-30 HU HU9500926A patent/HUT71090A/hu unknown
- 1995-03-31 PL PL95307952A patent/PL307952A1/xx unknown
- 1995-03-31 JP JP7097456A patent/JPH0841011A/ja not_active Withdrawn
- 1995-03-31 BR BR9501297A patent/BR9501297A/pt not_active Application Discontinuation
- 1995-03-31 CN CN95103977.6A patent/CN1112110A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3993692A (en) * | 1966-01-03 | 1976-11-23 | Stauffer Chemical Company | Methane sulfonyl chloride and process of preparation |
US3626004A (en) * | 1967-12-07 | 1971-12-07 | Pennwalt Corp | Method of preparing alkyl sulfonyl chloride |
US3600136A (en) * | 1968-08-26 | 1971-08-17 | Stauffer Chemical Co | Apparatus for producing methane sulfonyl chloride |
GB1350328A (en) * | 1971-05-28 | 1974-04-18 | Pennwalt Corp | Method for the preparation of alkane sulphonic acids |
EP0040560A1 (de) * | 1980-05-16 | 1981-11-25 | Societe Nationale Elf Aquitaine (Production) | Herstellung von Alkan-Sulfonyl-Chloriden |
EP0319767A2 (de) * | 1987-12-05 | 1989-06-14 | Bayer Ag | Verfahren zur Herstellung von Trifluormethansulfonsäurechlorid |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0894765A1 (de) * | 1997-07-31 | 1999-02-03 | Elf Atochem S.A. | Reinigung von Salzsäure, Nebenprodukt der Methansulfonsäureherstellung |
FR2766809A1 (fr) * | 1997-07-31 | 1999-02-05 | Atochem Elf Sa | Purification de l'acide chlorhydrique sous-produit de la synthese de l'acide methanesulfonique |
US6190635B1 (en) | 1997-07-31 | 2001-02-20 | Elf Atochem S.A. | Purification of the hydrochloric acid by-product of the synthesis of methanesulphonic acid |
WO2002010123A1 (de) * | 2000-08-01 | 2002-02-07 | Basf Aktiengesellschaft | Verfahren zur herstellung von alkylsulfonylchloriden und/oder alkansulfonsäuren |
CN1769160B (zh) * | 2004-06-30 | 2010-05-05 | 阿克马公司 | 甲磺酸合成中副产物盐酸的纯化方法 |
EP2386372A2 (de) | 2005-09-22 | 2011-11-16 | ATI Properties, Inc. | Vorrichtung für reine, schnell verfestigte Legierungen |
WO2017080994A1 (de) | 2015-11-10 | 2017-05-18 | Basf Se | Verfahren zur wiederaufarbeitung von alkansulfonsäure |
US10214485B2 (en) | 2015-11-10 | 2019-02-26 | Basf Se | Method of reprocessing alkanesulfonic acid |
US10577312B2 (en) | 2015-11-10 | 2020-03-03 | Basf Se | Process for purifying alkanesulfonic acids |
WO2018192954A1 (en) | 2017-04-18 | 2018-10-25 | Basf Se | Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride |
US10730827B2 (en) | 2017-04-18 | 2020-08-04 | Basf Se | Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride |
WO2018219726A1 (en) | 2017-05-30 | 2018-12-06 | Basf Se | Process for the production of alkanesulfonic acids |
US10894766B2 (en) | 2017-05-30 | 2021-01-19 | Basf Se | Process for the production of alkanesulfonic acids |
WO2019154681A1 (en) | 2018-02-07 | 2019-08-15 | Basf Se | Process for the manufacturing of alkanesulfonic acids |
US11247967B2 (en) | 2018-02-07 | 2022-02-15 | Basf Se | Process for the manufacturing of alkanesulfonic acids |
Also Published As
Publication number | Publication date |
---|---|
BR9501297A (pt) | 1996-02-27 |
PL307952A1 (en) | 1995-10-02 |
HU9500926D0 (en) | 1995-05-29 |
CN1112110A (zh) | 1995-11-22 |
JPH0841011A (ja) | 1996-02-13 |
HUT71090A (en) | 1995-11-28 |
CA2145325A1 (en) | 1995-10-01 |
IL113125A0 (en) | 1995-06-29 |
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